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A Geodynamic Thread
Enrique Merino and Amlan Banerjee1
Department of Geological Sciences, Indiana University, Bloomington, Indiana 47405, U.S.A.
(e-mail: merino@indiana.edu)
ABSTRACT
Although terra rossa has long been thought to form by residual dissolution of limestone and/or by accumulation of
detrital mud, ash, or dust on preexisting karst limestones, we present conclusive new field and petrographic evidence
that terra rossa forms by replacement of limestone by authigenic clay at a moving metasomatic front several centimeters wide. The red clays major chemical elements, Al, Fe, and Si, probably come from dissolved eolian dust.
The replacement of calcite by clay exhibits a serrated, microstylolitic texture that helps prove that replacement
happens not by dissolution-precipitation, as conventional wisdom has it, but by pressure solution of calcite driven
by the crystallization stress generated by the growth of clay crystals. The acid produced by the isovolumetric replacement of limestone by clay quickly dissolves out additional porosity/permeability in an adjacent slice of limestone
within the front, triggering a reactive-infiltration instability that should, theoretically, convert the moving reaction
front into a set of wormholes, then funnels, then sinksthe very karst morphology that in nature does contain the
terra rossa itself. This beautifully explains why terra rossa and karst are associated.
Introduction
have to be dissolved to yield a significant thickness
of terra rossa. According to the detrital theory, terra
rossa forms by accumulation of alluvial mud, volcanic ash, or eolian dust on limestones. A basic
problem of the hypothesis is that it does not account for the worldwide association of terra rossa
with karst carbonate rocks.
The purpose of this article is to propose a new
theory of terra rossa formation, by authigenic replacement of the underlying limestone at a narrow
reaction front. The new theory is based on field and
petrographic evidence on the terra rossa at Bloomington, Indiana. Since the clay is authigenic, its
major elementsAl, Si, and Femust come to the
front as aqueous ions. We propose that these aqueous ions probably result from dissolution of dust
at the surface. Taking account of recent insights
into the physics of mineral replacement (summarized in Replacement Physics) and into the dynamics of moving reaction fronts, we then show
that the clay-for-carbonate replacement, because it
generates acid, which dissolves out new porosity,
should trigger a morphological reactive-infiltration
instability, which theoretically specializes in
producing wormholes and funnels, precisely the
[The Journal of Geology, 2008, volume 116, p. 6275] 2008 by The University of Chicago.
All rights reserved. 0022-1376/2008/11601-0004$15.00. DOI: 10.1086/524675
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Figure 1. Reaction front between terra rossa and Salem Limestone at the construction site for Simon Hall, Indiana
University campus, Bloomington. The Salem Limestone is a coarse-grained calcarenite, here massive and horizontal.
The front thus cuts across bedding. It consists of a zone of bleached carbonate (zone A) 3 cm wide, containing a thin
subzone of opaques, and a zone of clay-for-calcite replacement (zone B) 6 cm wide. The labels 2a, 2b, 3a, etc.,
correspond to the approximate spots of photomicrographs in figures 2a, 2b, 3a, etc.
ible in zone B (fig. 1b). The bleached zone A contains a thin subzone of opaque grains of a Mn oxide.
The Mississippian Salem Limestone is a massive
calcarenite consisting mostly of coarse crinoid and
bryozoan fragments cemented by clear calcite;
chemical analyses provided by the Indiana Geological Survey indicate that the unaltered Salem contains small amounts of Al, Mn, Si, and Fe, generally
less than 1 wt% of their oxides.
Petrography, Zone B. The field evidence of a replacement-and-bleaching front is confirmed by petrographic analysis of six thin sections from samples
from the front. (Another 60 terra rossa samples not
from the front have been examined petrographically, and about 25 of them have been studied magnetically.) Figure 2c shows a circular crinoid columnal from the replacement zone that is partly
replaced by an orange clay aggregate that preserves
the shape and volume of the replaced portion of the
crinoid, a feature characteristic of replacement. Fig-
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Figure 2. Petrography of the leaching and replacement zones. The site of each photomicrograph is marked in figure
1. a, Unaltered Salem Limestone consists of bryozoans and equinoderm fragments (black arrows) well cemented by
clear calcite cement. Plane-polarized light. b, Dissolution voids (see also those in the unreplaced portion of the crinoid
in c) are produced in the bleaching zone by leaching of calcite driven by the H released by the replacement taking
place in zone B, reaction (1). Crossed polars. c, Circular crinoid columnal at center is partly replaced by orange
kaolinite (black arrow) in the replacement zone (B) of figure 1. The circular shape of the replaced portion is roughly
preserved, indicating isovolumetric replacement, a fact used in adjusting reaction (1). The crinoid was slightly leached
when it was in the bleaching zone (A), before it started to be replaced. The leaching can be seen in the unreplaced
portion (white arrow) of the calcitic columnal. Plane-polarized light. d, A fairly mature iron oxide pisolite from far
behind and above the front, surrounded by terra rossa clay. Both pisolite and clay contain many quartz silt grains,
probably left undissolved from dissolution of eolian dust and worked into the terra rossa pedologically; see Elements
Making Up the Red Clay Probably Come from Dissolved Dust. The pisolite grew slowly (from an incipient precursor
like the one in fig. 3a), replacing the surrounding clay and incorporating its quartz silt grains. Plane-polarized light.
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Figure 3. Clay-for-calcite replacements in zone B of the terra rossa front. Sites of the photomicrographs are marked
in figure 1. Zone B is the zone of current replacement. a, Large orange clay aggregate (between arrows) partly replaces
the center of a plate of calcite cement in zone B, leaving two still-unreplaced portions (crosses), one on each side.
The crinoid at center is also still unreplaced. The clay aggregate contains an incipient, fuzzy iron oxide pisolite (pi)
that has crystallized recently, like the clay itself. b, Same as a, under crossed polars, showing that the two portions
of unreplaced calcite cement are in optical continuity and that the clay aggregate consists of interlocking crystals,
indicating that the red kaolinite is authigenic. c, Brown clay starts (at arrow) to replace a crinoid fragment, producing
a striking serrated texture (Pettijohn 1957, p. 674) also evident in figure 4a and throughout the replacement zone B;
see Petrography, Zone B. Plane-polarized light. d, Same as c, under crossed polars, showing the large size of some
of the authigenic clay crystals by the size of areas with one birefringence (arrow).
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Local Mass Balance upon Replacement. The constant-volume replacement of calcite by clay (here
assumed to be pure kaolinite for simplicity) can be
written as
immediately bleaches and dissolves voids in an additional slice of limestone, zone A. When the unreplaced calcite in todays replacement zone B is
completely replaced in the near future, replacement
will start in what is today the bleached zone, A, and
the acid generated there will start leaching and
bleaching what is today still fresh limestone just to
the left of zone A in figure 1b. This is how the metasomatic front moves across the limestone, leaving
behind (and/or above) it a trail of terra rossa that is
increasingly older the farther it is from the front.
(1)
Journal of Geology
(2)
(3)
which also produces acid that would help that produced by reaction (1) to generate the next leaching
zone. As noted in Discussion, this cement may
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interfere with the operation of the reactive-infiltration instability (see The Reactive Infiltration
Instability and the Origin of Karst), by plugging
some of the porosity/permeability created by the
leaching.
Elements Making Up the Red Clay Probably
Come from Dissolved Dust
Many investigators, cited in Previous Work on
Terra Rossa, have shown that specific terra rossa
formations contain chemical elements that can be
traced to elements in eolian dust, confirming the
fact that eolian dust must settle on the earths surface. But since the red clay making up terra rossa
is authigenic, as shown in figures 1, 3b, and 3d, the
Al, Fe, and Si needed to make the clay crystals must
be supplied to zone B as aqueous ions. We therefore
suggest here that the aqueous Si, Fe, and Al supplied to the front come from the dust fraction that
is dissolved at the surface of the existing terra rossa
and then delivered, by infiltration, to the front a
few meters below. Acid rain and soil water would
quickly dissolve the finest fraction of the dust,
which presumably is clay rich. In support of this
idea is the following petrographic evidence.
If the finest dust is dissolved, the undissolved
fraction, in general mainly quartz (and feldspar) silt,
should be left on the terra rossa and would be
worked into it pedologically. (The quartz silt would
be insoluble in the soil pore water, enriched in silica by dissolution of the finest dust fraction.) Indeed, we have seen (fig. 2d) scattered quartz silt in
many thin sections of Bloomington terra rossa.
The Reactive-Infiltration Instability
and the Origin of Karst
Where a reactive fluid both flows through a porous
rock and partly dissolves it, a porosity-making front
is established that was quantitatively predicted in
the 1980s and 1990s to become fingered (Chadam
et al. 1986; Ortoleva et al. 1987; Aharonov et al.
1997); see figure 6A. The dissolution increases porosity/permeability, which accelerates advection of
reactive water. In turn, the faster advection accelerates further dissolution. This is the reactiveinfiltration instability. It works as follows. Any
higher-than-average porosity/permeability in a volume element of the front, such as at point a in
figure 6A, captures flux from the neighbor elements. Dissolution thus accelerates at a, increasing
its porosity/permeability even more, drawing still
more flux from the neighbor elements and producing a high-permeability finger. Simultaneously, the
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rosity/permeability fingers. (This competitive morphological dynamics also takes place in the completely different context of quartz growth within
agates in basalts; see Wang and Merino 1995. In
that case, the fingers of the instability are the
quartz fibers themselves, which make agates invariably fibrous.) After the terra rossa front has become fingered, the competition for reactive flux
continues among the fingers themselves, leading to
successive jumps in the spacing and size of the fingers (Szymczak and Ladd 2006). The predicted cascade of scales is shown schematically in figure 6B.
From being a set of advancing fingers, the front
passes to being a set of funnels one order of magnitude larger than the fingers. In turn, the funnels
later jump to sinks an order of magnitude greater
in size and spacing than the funnels.
The reaction front we have discovered between
terra rossa and the underlying Salem Limestone appears to be a natural case of the kind of moving
porosity-making front whose dynamics is described
above and in figure 6. The instability-triggering dissolution is the leaching (eq. [2]) carried out in the
bleached zone by the acid released by reaction (1)
in the replacement zone. The replacement-plusbleaching front should therefore become fingered
as it advances into limestone, and the fingers
should jump to funnels and these to sinkholes. But
these predicted forms coincide with the morphological features that are characteristic of karst carbonates (e.g., Thornbury 1954; White 1988; Donovan 2002; Twidale 2004). We thus arrive at the
surprising realization that the terra rossas authigenic clay indirectly makes the very karst limestone morphology that contains it, which explains
why the two are associated.
The singularity and separation between karst
funnels or sinks are traditionally attributed to the
focusing of descending acid water by intersecting
fractures, which are conveniently assumed to have
the spacing required to produce the observed sinkhole spacing (e.g., White 1988; Twidale 2004). Admittedly, limestone dissolution would be faster at
the intersection of two subvertical fractures, giving
rise to a funnel or sink, but intersecting fractures
are an accidental feature, one that cannot be
counted on systematically to determine the location of every sink of every karst, and furthermore,
the assumed intersecting fractures have to have the
required spacing to produce the observed spacing
between karst features. (Most concavities in many
floaters in Bloomingtons front yards do not exhibit
intersecting fractures; see fig. 6C.) On the other
hand, the reactive-infiltration instability is a mechanism triggered internally, and it automatically
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